Wool or hair treated with methacrylic anhydride or itaconic anhydridecopolymerized with maleic anhydride and after treated with mercaptoethylamine and propylene diamine or butyl amine

ABSTRACT

Human hair and wool are treated with a water or aqueous alcoholic solution of a polysulfhydryl copolymer having a molecular weight of 1,000 - 20,000.

0 United States Patent 1 m1 3,762,863

Charle et al. Oct. 2, 1973 WOOL 0R HAIR TREATED WITH abandoned.

METHACRYLIC ANHYDRIDE 0R ITACONIC ANHYDRIDE COPOLYMERIZED I52] 0.8. CI. 8/1275], 8/1276 WITH MALEIC ANHYDRIDE AND AFTER A6lk 7/10, 006m 3/06 TREATED WITH MERCAPTOETHYLAMNE [58] Field of Search 8/3l l()(), l27.6, AND PROPYLENE DIAMINE 0R BUTYL 17; 260/78 UA AMINE [75] Inventors: Roger Charle, Soisy sur [56] References cued Montmorency; Gregoire Kalopissis; UNITED STATES PATENTS Andri" vim", both of Paris; 3,576,592 4 1971 Zviak 8/128 A Constantin Aretos, lssy-lesmoulineaux; Jean Gascon, Paris, all of France Assignee: Societe anonyme dite: LOreal, Paris,

France Filed: Jan. 13, 1972 Appl. No.: 217,650

Related US. Application Data Continuation of Ser. No. 831,711, June 9, 1969,

Primary ExaminerD0nald Levy Attorney-Cushman, Darby & Cushman ABSTRACT 2 Claims, No Drawings WOOL OR HAIR TREATED WITH METHACRYLIC ANHYDRIDE OR ITACONIC ANHYDRIDE COPOLYMERIZED WITH MALEIC ANHYDRIDE AND AFTER TREATED WITH MERCAPTOETHYLAMINE AND PROPYLENE DIAMINE OR BUTYL AMINE This is a continuation, of application Ser. No. 831,711, filed June 9, 1969, and now abandoned.

SUMMARY OF THE INVENTION It has already been suggested that keratinic fibers, and particularly human hair be treated with sulfhydrylated polymers which are derived from the condensation of aminothiols with certain types of polymers having acid anhydride groups in their chains, which are capable of reacting with the amino group of the aminothiol to produce an amide bond.

Among the polymers which will react with an aminothiol which have already been suggested are: the copolymers resulting from the copolymerization of maleic anhydride with various types of ethylene monomers such as olefines, and vinyl, acrylic, and methacrylic derivatives, and homopolymers resulting from the polymerization of an unsaturated acid anhydride.

The present invention relates to new polysulfhydryl polymers which may be advantageously used to treat keratinic textile fibers in order to improve their own properties and also to facilitate their dyeing, and particularly with reactive dyes.

It is an object of the present invention to provide as a new article of manufacture a polysulfhydryl copolymer characterized by the fact that it comprises:

Constituents 1 having the following formula:

in which:

A represents a component selected from the group consisting of:

.1. UK I T l l l in which R, R and R represent either hydrogen or a lower alkyl radical and R", represents a lower alkyl radical;

and constituents Il responding to the formula:

the constituent:

in which R and R represent either a hydrogen atom or a lower alkyl radical, R represents either a hydrogen atom, a lower alkyl radical, -ococH,, COOCH CN, or an alkoxy radical,

M may be identical or different for each constituent and is selected from the group consisting of:

a remainder having a thiol function,

a hydrocarbon remainder which may have an amine function, it being understood that for at least 1 percent of the constituents M signifies a remainder rcprescnting a thiol function.

In the above definitions and throughout the specification lower alkyl is an alkyl having 1-6 carbon atoms, such as CH C H etc. and alkoxy is an alkoxy having 1-6 carbon atoms such as -OCH OC l-l etc.

The polymers according to the invention must be soluble in water and lower molecular weight volatile alcohols such as ethanol and propanol. They have molecular weight generally comprised between 1.000 and 20.000.

ln a particular embodiment, the copolymer may also contain one or more types of constituents different from constituents l and 11 and selected from the group consisting of the possible constituents of group 11.

in a preferred embodiment of the invention, the constituents l are derived from the polymerization of an unsaturated organic anhydride selected from the group consisting of itaconic anhydride, citraconic anhydride, acrylic anhydride, methacrylic anhydride, a mixed acrylic/methacrylic anhydride, which is condensed by amidification with an amino-thiol, a monoamine, or a diamine.

In a preferred embodiment of the invention, the constituents 11 are derived from the polymerization of an unsaturated ethylene monomer selected from the group consisting of maleic anhydride, itaconic anhydride, citraconic anhydride, acrylic anhydride, methacrylic anhydride, mixed acrylic-methacrylic anhydride, olefines having from 2 to 8 carbon atoms, acrylic, methacrylic and vinyl derivatives, such as esters, amides, nitriles of acrylic or methacrylic acid, and esters or ethers of vinylic alcohol.

Among the amino-thiols which may be amide bonded to form the remainder M are:

those aminothiols having the formula HS-R-NH-R' in which R represents an alkylene radical preferably comprising 2 to 4 carbon atoms, which may be substituted either by lower alkyls which may have up to 4 carbon atoms, or by a carboxyl radical or by a carbalkoxy group which radical or group may have 1-5 carbon atoms, and

R represents a hydrogen atom or a lower alkyl such Among the aminothiols corresponding to the foregoing formula are:

B-mercaptoethylamine,

cysteine, and

ethyl cysteinate Among the amino-thiols which may be amide bonded to form the remainder M are the mercapto-amide amines having the formula:

l 1-IN-c11 crn)qENn-co-cm-mrnhJ-sn in which:

R represents H, CH C l-l or Ch CH -OH,

R represents H or COOH,

q is a whole number between 1 and 5 inclusive,

q. equals 0 or 1,

p equals 0 or 1.

Among the mercapto-amide amines corresponding to this last formula are those derived from thioglycolic acid esters, thiolactic acid esters, Bmercaptopropionic acid esters, and from diamines such as ethylene diamine, hexamethylene diamine, and N-hydroxyethyl ethylene diamine.

In accordance with the invention, the remainder M may also be derived from amines having no -Sl-l groups. This makes it possible to reduce at will the concentration of -SH groups in the polysulfhydryl homopolymers, while at the same time introducing into the polymer groups which impart particular properties thereto.

Thus for certain constituents M may be derived by amide bonding of compounds responding to the formula in which R represents hydrogen or a lower alkyl, R represents a lower alkyl or a radical having the formula in which r and r are identical or different lower alkyls, or may form part of a heterocyclic ring such as that of morpholine or piperidine.

m is a whole number between 0 and '4 inclusive.

Among the compounds responding to the above formula are 'butylamine, N,N-diethylpropylene diamine and N-(B-aminoethyl) morpholine, but this list is merely representative and not exhaustive.

All M groups can be thiols groups.

Nevertheless when partially polysulfhydryl compolymers are produced according to the invention, the proportions of mercapto-amine in a given homopoly' mer may be varied within broad limits ranging for example from 1 to 99 percent, but preferably 20 to 80 percent of the totality of the remainder M the copolymer according to the invention must contain at least 1 percent of SH function as regard as the total amount of anhydride functions fixed on the copolymer.

it is a further object of the present invention to provide a method of preparing a polysulfhydryl copolymer such as described above, which method is characterized by the fact that two different unsaturated monomers belonging to the above groups are first copolymerized, after which the aminothiols and amines corresponding to the desired formula are condensed on the resulting copolymer.

Another embodiment of the process according to the invention may also include the copolymerization of unsaturated diacid monomers derived from the abovedefined anhydride monomers, the diacid functions being transformed into acid anhydride functions, to which at least one aminothiol such as above described is amide bonded.

ln yet another embodiment of the process according to the invention an aminothiol or amine is attached to an unsaturated anhydride monomer of the type above described and the resulting monomers are then copolymerized.

lt is a further object of the present invention to pro vide as a new article of manufacture a composition for treating the hair, wool and other keratinic fibers which is essentially charactrized by the fact that it contains at least one polysulfhydryl copolymer of the type described above.

In a preferred embodiment of the invention the composition contains from 1 to 10 percent and preferably 2 to 5 percent by weight of the polysulfhydryl copolymer.

The pH value of the compositions according to the invention may advantageously fall between 7 and 9 in elusive.

' The cosmetic composition may also contain any type of cosmetic ingredient, such as swelling agents, surfaceactive agents, perfumes and resins.

This cosmetic composition according to the invention may take the form of an aqueous or hydroalcoholic lotion and serve as a hair setting lotion, It may .also take the form of a cream or gel or be packaged as an aerosol in a liquefied hydrocarbon mixture.

The present invention also relates to a new method of treating keratinic textile fibers, particularly in order to facilitate their dyeing with reactive or metalliferous dyes. This process is essentially characterized by the fact that the keratinic textile fibers are impregnated with a polysulfhydryl copolymer as hereinbefore defined.

It is a further object of the present invention to provide a new method of dyeing keratinic fibers characterized by the fact that the fibers are impregnated with a solution of at least one copolymer as hereinbefore defined, after which the fibers are dyed with at least one dye selected from the group consisting of reactive and metalliferous dyes.

It is a further object of the present invention to provide the new article of manufacture which consists of keratinic fibers characterized by the fact that they have been impregnated with a polysulthydryl copolymer as above described.

Yet another object of the invention is to provide as a new article of manufacture keratinic fibers characterized by the fact that they have been dyed by reactive or metalliferous dyes after having been impregnated by a copolymer such as has been defined above.

In order that the invention may be better understood, several methods of preparing copolymers according to the invention will now be described, purely by way of illustration and example.

EXAMPLE 1 Preparation of a 50 percentrnaleic anhydride 50 percent itaconic anhydride copolymer (in terms of weight).

The following starting materials are placed in a oneliter flask equipped with a stirring rod, a reflux condenser, a thermometer, a dropping funnel and a tube for introducing nitrogen: 4

maleic anhydride 60 g itaconic anhydride 60 g distilled benzene 300 cc EXAMPLE 2 Preparation of a 75 percent maleic anhydride-25 percent methacrylic anhydride copolymer (in terms of weight).

The followingstarting materials are placed in a oneliter flask equipped with a stirring rod, a reflux condenser, a thermometer, a dropping funnel, and a tube for introducing nitrogen:

maleic anhydride 75 g distilled benzene 240 cc benzoyl peroxide 5.882 g This is heated to reflux and 25 g of methacrylic anhydride is introduced drop by drop over a period of 12 hours.

The resulting polymer is filtered, washed with pentane, and dried.

The yield of the reaction, by weight, is 60 percent.

Analysis shows that the anhydride index is 1,046. The theoretical anhydride index is also 1,046.

EXAMPLE 3 Preparation of a polysulfhydryl copolymer having the formula:

orrcn cnzc (|3H(|3H l CHHJ l ()OOH b0 00 COOH C0 C0 2 CH2 l NH H NH NH 000151 I I COOH CH2 $112 (1H1 (3H7 Hz (3H2 (3H2 $112 AH CH: (3H2 SH H01 N N HCl 02H: CzHs (32H: C2Hs 2 n B-mercaptoethylamine and N,N-diethyl propylene diamine are condensed on the maleic anhydride/itaconic anhydride copolymer prepared in Example 1.

37.8 g (1/3 gram mole) of B-mercaptoethylamine hydrochlorid and 250 ml of water, followed by 86.6 g (2/3 gram mole) of N,N-diethyl-propylene diamine are introduced into a flask equipped with a stirring rod, a thermometer, a dropping funnel, and a tube for introducing nitrogen.

13.3 g (1/3 gram mole) of sodium hydroxide in tablet form are than added while cooling so as to liberate the amine from its hydrochloride. 56 g (0.5 gram mole) of the copolymer prepared in Example 1, followed by 20 g (0.5 gram mole) of sodium hydroxide tablets, are then added, while stirring and cooling, to liberate the amine contaminating the carboxyl of the polymer.

56 g (0.5 gram mole) of the polymer and 20 g (0.5 gram mole) of sodium hydroxide tablets are then added simultaneously.

When the reaction has been completed, the reaction medium is acidified by adding concentrated hydrochloric acid, which precipitates the polymer. The product precipitated is washed in water and then vacuum dried.

The result is a yield of 50% by weight of the desired end product. The following tests were carried out on this polymer which, after drying, is a powder which is soluble in water at alkaline pH values.

- Calculated Found Corrected Found Cl total 9.46 7.19 2.94 NaCl 0 7.00

Free SH 4.40 1.48-1.50 1.59-1.61

Total SH 2.07-2.07 2.21-2.23

EXAMPLE 4 A polysulfhydryl polymer according to the invention and having the following formula is prepared:

I I c0011 '00 coon 0 OH 1 TH NH NH CH: Da 9a CH: (ill-Ia G H: 2

by condensing B-mercaptoethylamine and butylamine on a maleic anhydride/methacrylic anhydride copolymer prepared as described in Example 2.

The procedure is the same as in Example 3, except that the N,N-diethylpropylene diamine is replaced by an equimolecular quantity of butylamine. The yield is 60 percent by weight of a powder which is soluble in water at an alkaline pH, and on which the following analytical tests were carried out:

I: found after Calculated I: Found correction due to NaCl Free SH 6.07 l.20-l.40 L34 Total SH 2.60-2.90 2.84 NaCl 3.21

EXAMPLE 5 Preparation of 50 percent vinyl acetate 50 percent citraconic anhydride copolymer The following products are introduced into a oneliter flask equipped with a stirring rod, a reflux condenser, a thermometer, and a tube for introducing nitrogen:

vinyl acetate 50 g citraconic anhydride 50 g toluene distilled 233 cc benmyl peroxide 5.882 g This is heated to reflux while stirring under a nitrogen atmosphere. The resulting copolymer precipitates in the toluene. The operation comes to an end after 8 hours. The product is washed with petroleum ether and dried.

The copolymer is in the form of a powder.

The yield of the reaction is 86 by weight.

The anhydride index of the resulting product is 563.5, against a theoretical index of 500. The end product comprises 43.7 percent vinyl acetate and 56.3 percent citraconic anhydride by weight.

EXAMPLE 6 Preparation 50 percent isobutylvinyl ether, 50 percent itaconic anhydride copolymer The following starting materials are introduced into 7 a one liter flask equipped with a stirring rod, a reflux (10 1 111 6H, CH1.

S H u condenser, a thermometer, and a tube for introducing nitrogen:

isobutylvinyl ether 50 g itaconic anhydride 50 g distilled toluene 233 cc benmyl peroxide 5.882 g This is heated to reflux while stirring under a nitrogen atmosphere.

After 8 hours, a reddish viscous solution is obtained. The resulting polymer is precipitated with petroleum ether, and dried. This polymer is in the form of a red powder. The yield of the reaction is 80 by weight. The anhydride index of the reaction product is 572 against a theoretical index of 500. The polymer comprises 42.8 percent by weight of isobutylvinyl ether groups and 57.2% by weight of itaconic anhydride.

EXAMPLE 7 Preparation of 75 percent methyl acrylate 25 percent acrylic anhydride copolymer The following starting materials are introduced into a one-liter flask equipped with a stirring rod, a reflux condenser, a thermometer, and a tube for introducing nitrogen.

methyl acrylate 75 g acrylic anhydride 25 g toluene 300 cc benzoyl peroxide 5.882 g This is heated slowly to reflux while stirring under a nitrogen atmosphere. After 8 hours, the yield is a powder which is drained, washed with pentane, and dried. The copolymer is in the form of a white powder. The yield of the reaction is percent by weight. The anhydride index of the resulting product is 374, against a theoretical index of 222. The polymer comprises 58 percent by weight of methyl acrylate groups and 42 percent by weight of acrylic anhydride groups.

EXAMPLE 8 Condensation of B-mercapto-ethylamine and N,N- diethyl propylene diamine on a vinyl acetate/citraconic anhydride copolymer prepared as in Example 5 The following copolymer is prepared:

duced into a flask equipped with a stirring rod, a thermometer, a tube for introducing nitrogen and a drop- Calculated found Corrected ping funnel. 20 g (one-half gram mole) of sodium hydroxide are then added to liberate the amine. 99 g (0.5 gig 2 8253 O 394) 40 gram mole) of vinyl acetate/citraconic anhydride coms 1:16-1:18 1:224:24 polymer is then added while stirring and cooling. 10

After having introduced the ol mer into the flask, A r 20 g (0.5 gram mole) of sodiurr i hydroxide tablets are EXAMPLE l0 added to the reaction mixture, little by little. The 99 g Condensatlon of B mer capt0cthy|amme on a methyl (0.5 gram mole) more of the vinyl acetate/citraconic acrylatelacryllc anhydnde copolymer prepared as anhydride copolymer is added, followed by 20 g more Example 7 to produce a polysulfhydryl copolymer of sodium hydroxide tablets, added little by little. havmg the fmmula? At the end of 3 to 4 hours, the reaction ends and the end product is isolated by acidification and precipitation out with sodium chloride. CH1CH*CH1 CHCHICH The result is 184 g of the desired copolymer in the OOCH; COOH =0 form of a powder which is soluble in water at a neutral NH or alkaline pH value. This corresponds to a yield of about 60 percent. CH] The final polymer contains 10 percent sodium chlo- I s11 ride. n

This resulting product is purified by dissolving it in a mixture of dimethylformamide and alcohol, the insoluble sodium chloride being eliminated by filtration. The The procedm-e is the Same as in Example 3 except desired product is precipitated from the filtrate by addthat 1 gram l f B mercaptoethy|amine i ing etherdensed on 1 gram mole of methyl acrylate/acrylic anhy- The following analyses of the end P were dride copolymer. The yield is 83 percent by weight of made: a gum which, after purification, takes the form ofa pulverulent mass which is soluble in water at a neutral of Calculated Found found as correctalkaline PH ed on accournxtigll" Analysis of this product showed the following results:

gla 3' 3 Calculated Found first; did-25 did Total SH 5.80-5.65

EXAMPLE 9 Examples of Application Condensation of B-mercapto-ethylamine and butylamine on an isobutylvinyl ether/itaconic anhydride Exampie A copolymer prepared as in Example 6 to produce a A -"l 1on0 to the mvennonha polysulfhydryl copolymer having the formula: mg the following composition is prepared:

[- "HQ-OH Ha-C Hi-C CHI C 1 (I) C \C=O (I) C 1 0:0 (3H2 OOH I IH (iH: (BOOH I IH do do, do do, H;C/ cm (in, H3O \CHJ 01H; do. S'H (EH3 2 u The procedure is the same in Example 8 except that P fi i Obtaineg in Example 4 H 3% one-third gram mole of B-mercaptoethylamine and 2.132 15? dg two-thirds gram mole of butylamine is condensed on 1 p rfum 0.2 g gram mole of isobutylvinyl ether/itaconic anhydride (154" 100 cc copolymer.

The result is a yield of -85 percent by weight of a gum which, after purification with dimethylformamide, precipitation with ether, and drying, takes the form of a powder which is soluble in water at a neutral or alkaline pH.

The end product was analyzed, with the following results:

The resin is first dissolved in the water in the presence of aminoethylpropanediol. The ethyl alcohol and perfume are then added. The pH value is adjusted with the above base and the lotion completed by adding enough water to make up the indicated volume.

In order to set the hair, 20 cm of this lotion is applied to hair which has been washed and dried. The hair is then combed to spread the lotion, wound up on rollers, and dried. After unwinding, the hair is combed, and a set of excellent quality results.

Example B A solution having the following composition is prepared as in Example A:

copolymer produced as in Example 9 3.5 g aminoethylpropanol q.s.p. pH 7 ethyl alcohol q.s.p. 50 water q.s.p. 100 cc copolymer produced as described in Example 8 3 g aminothylpropanol q.s.p. pH=8 ethyl alcohol q.s.p.20 water q. s.p. l cc Equally good results are obtained with respect to the holding power of the hair set.

The following solutions may be used to impregnate keratinic fibers as set forth in the following examples. Solution l polysulfhydryl copolymer produced as described in Example 3 3 g solution of ammonia at 22 Be 4,5 35; water g.s.p. l00cc Solution ll polysulfhydryl copolymer produced as described in Example 10 l,l g solution of ammonia at 22 Be 2 cc water q.s.p. 100cc Example D v 4 g of woolen yarn is treated with solution l by immersing it therein at room temperature for minutes. After drying, the yarn is rinced in an N/l0 solution of acetic acid and dyed by immersing it in a dyeing solution containing:

5 when being dyed.

The result is a blue coloration. Example E 4 g of woolen yarn is immersed in solution ll for 15 minutes at room temperature. After drying it is rinsed 0 with N/lO solution of acetic acid, and dyed by immersing it in a dyeing solution containing:

Reactive red 7 6.1 0.12 g glacial acetic acid 2 cc water q.s.p. 200 cc The dyeing is carried out at 80 C for 60 minutes. The wool is rinsed copiously in water and scoured at 50 C for minutes in a 2 solution of ammonia. It is again rinsed and boiled in the manner conventional in the 20 case of wool.

An attractive red coloration results.

Similar dyeing results are obtained on other types of keratinic fiber such as human hair, for and animal hairs other than wool, etc., and improved keratinic fiber dye- 5 ing occurs using other keratinic fiber dyes such as reactive dyes, or metalliferous dyes, and dyes such as Acid Green 12 Cl l3425, and Black 43 Cl l5,69l, etc., and the various reactive dyes set forth in copending application Ser. No. 441,311, filed Mar. 19, 1965.

All of the polymers that have the constituents I and ll are soluble in water and/or volatile alcohols, such as ethanol, propanol, etc., and they all may be used to treat human hair and other keratinic fibers and to improve the dyeability of keratinic fibers such as wool 5 with reactive dyes or other types of dyes.

Our tests show that the substituted groups A, R, R, R", R', B, R,, R R M, etc., defined above, do not prevent the critical solubilizing action of the COOH groups and the reducing action of the SH groups on the 0 polymer.

What is claimed is:

l. A process for treating human hair comprising applying to said hair effective amounts of a composition comprising a solution in a solvent selected from the group consisting of water and an aqueous alcohoiic solution of l-l0 percent by weight of a polysulfhydryl c0- polymer having a molecular weight between L000- 20,000, said polysulfhydryl copolymer being selected from the group consisting of -(3H- -oH-cHlO-(lJH-CH-- cHlC 1 00H 0:0 0:0 COOH (8:0 (3:0

2 l CH2 1 NH NH NH I 1 00 011 l 1 00 OH 1 H2 H: CH; CH1 din CH; H: H2 H H: H, H

HCl-N /N-HCl HsC: C235 HsCz CaHs 2 Reactive Blue 2 or 0.12 g and glacial acetic acid 2 cc. b. polysulfhydryl polymer having recurring units of water 200 cc the formula l I CH3 CH3 CH! CH3 I CHCH-cH,-:CH1-CHCH-cH,-t )-CH,-G

(IJOOH 3:0 (IJOOH :0 COOH C=O OOH =0 11TH I IH NH I1IH ICH: lHah (iJHz): (13H: H2 (1H3 (3H3 2 H; L $11 in said composition having a pH of 7-9, winding said a. polysulfhydryl polymer having recurring units of hair on rollers and drying said hair. the formula CH -(JH- CH,(: CH CH "Hi-C 1 JOOH (3:0 C=O (300K (3:0 C=0 NH CH2 11m I IH CH2 1 m COOH I 1 COOH CH1 CH: CH; CH; (3H JH, CH; H C'H, C'H, in

HCI-I J I I'HCI Hscz \C1H5 HsCz C2Ha 2 2. A process for treating wool comprising immersing and said wool in a composition comprising a solution in a b. polysulfhydryl polymer having recurring units of solvent selected from the group consisting of water and the formula I- am CH; CH1 CH3 -CH--CI'ICHJ( JCHQ( JCH-CHCH1CHj-C COOH C=O ('10011 3:0 (IOOH C=0 COOH (3:0

b IH Rm 1 111 in; CH: lHzk (411193 3112 H: C IHa H: 2 (13H: SH SH an aqueous alcoholic solution of 1-10 percent by said composition having a pH of 7-9, drying said weight ofa polysulfhydryl coplymer having a molecular 40 wool and rinsing said wool with N/lO solution of acetic weight between 1,000 20,000 said polysulfhydryl coid polymer being selected from the group consisting of UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3, 7 3 Dated October 973 Roger Charle, Gregoire Kalopissis, Andre Viout, Inventor) Constantin Aretos and Jean Gascon It is certified that error appears in the above-identified patent and that said Letters Patent are hereby corrected as shown below:

In the Heading, Andrio Viout" should read --Andre Viout-.

Please insert --Claims priority, application France,

June 10, 1968, No. 15 5407.

Column 9, the structural formula between lines &8-60 should read:

- CH CH T 0H o 0H CH CH c l r I 3 CH C= CH COOH NH lCH COOH NH l CH CH CH CH H C CH (3H H C CH H Signed and sealed this 2nd day of April 197M.

(SEAL) Attest:

EDWARD M.FLETCHEH,JR. I C. MARSHALL DANN Attesting Officer Commissioner of Patents M PO-1050 (10-69) USCOMM-DC 60376-969 q u 5. covtluunn "mums orncr I!!! 0-366-JN 

2. A process for treating wool comprising immersing said wool in a composition comprising a solution in a solvent selected from the group consisting of water and an aqueous alcoholic solution of 1-10 percent by weight of a polysulfhydryl coplymer having a molecular weight between 1,000 - 20,000 said polysulfhydryl copolymer being selected from the group consisting of a. polysulfhydryl polymer having recurring units of the formula 